1

Rhenium in Nuclear Fuel Cycle

Plenary lecture at ISTR2011

Troshkina I. D.

D. Mendeleev University of Chemical Technology of Russia

2

Stages of the Nuclear Fuel Cycle

3

RHENIUM IN THE NUCLEAR FUEL CYCLE

1. Associated rhenium recovery in uranium mining and hydrometallurgical processing

2. Rhenium-containing alloys - structural material of high temperature reactors

3. Rhenium as isotope production for nuclear medicine

4. Rhenium - a simulator of technetium in research

4

PRODUCTION OF RHENIUM

05

101520253035404550

1940

1944

1950

1955

1960

1965

1970

1975

1980

1985

1990

2005

2007

Re,

ton

Main producing countries: Chile, USA, Poland, China, CIS (Kazakhstan, Uzbekistan, Armenia)

5

The dynamics of the rhenium global market((www.roskill.comwww.roskill.com//reportsreports//minorminor--andand--lightlight--metalsmetals//rheniumrhenium, 2010 , 2010 гг.).)

The annual consumption of rhenium in 2015 will reach morethan 70 t

6

Background- USA1969-1974, Falls City, Texas area bySusquehanna Corporation → ShattuckChemical in Denver- Former USSR1978, Central Asia, Bukinayskayagroup, underground leaching

7

Rhenium in the uranium ores

- Deposits of the sedimentary type- Stratum-infiltration exogenous deposits

Type of the deposit

Deposit Rhenium content, g/t

Sedimentary Colorado Plateau(Sun Valley)

0.5 –3.0

Stratum-infiltration South Dakota Up to 50

8

Deposits of the Prityanshanskaya Province

Deposits: 1 - Uchkuduk, 2 - Sugraly, 3 - Ore, 4 - Sabyrsay, 5 - Bukinay, 6 - Southern Bukinay, 7 - Ketmenchi, 8 - Lyavlyakan, 9 - Beshkak, 10 - North Kanimeh, 11 - Varadzhan, 12 - Terekuduk, 13 - Aland, 14 Koscheka, 15 Dzhantuar, 16 - North Karamurun, 17 - South Karamurun, 18 - Irkol, 19 Kharasan, 20 - Kyzylkol, 21 - Lunar 22 - Chayan, 23 Zarechnoye, 24 - North Mayzak 25 - Schark, 26 - Jalpak, 27 - Mynkuduk, 28 - Uvanas, 29 - Kanzhugan, 30 -Inca 31 - Moinkum, 32 - Tortkuduk, 33 - Budyonnovsk, 34 - Agron, 35 - Asarchik, 36 -Meylysay 37 - Bahaly, 38 - Aktau, 39 - Kendyktyube(In-Situ Leaching of Ores / N.P. Laverov et.al. M., 1998)

9

KyzylkumKyzylkumoreore

districtdistrict

10

ZonationZonationReRe--ScSc--SeSe--mineralizationmineralization

inin thethe contourcontour ofof thethe uraniumuraniumbodybody

KanimehKanimeh depositdeposit, , UzbekistanUzbekistanВмещающие породы

Урановое оруденение

Неполноеи полное окисление

Eh,B

0 1а 1б 1в2а 2б 2в 2г

ба

Eh

Подзоны

Ph

0,4

0,20

9876

Ph

Se

URe

Sc

50 0 50 150 м

5

0

5

15

25

35

11

The rhenium content in uranium ores (the Prityanshanskaya Province)(In-Situ Leaching of Ores / N.P. Laverov et.al. M., 1998)

Province The uranium content, %

The rhenium content, g/1000 kg

Central Kyzylkum 0,01-0,1 0,5-2 (to 15)

Syr-Darya 0,01-0,1 0,02-1

0,03-0,05 0,1-0,5

Central Kyzylkum Province - North Field Bukinay, South Bukinay, Beshkak, Ketmenchi, SabyrsaySyr-Darya Province - North Karamurun deposit, South KaramurunChu Sarysu - deposits Uvanas, Kanzhugan, Mynkuduk, Moinkum

Chu Sarysu

12

ForecastingForecasting--metallogenicmetallogenic mapmap ofof rheniumrheniumdepositsdeposits ofof RussiaRussia

(IMGRE, (IMGRE, KremenetskyKremenetsky АА..АА. . andand othersothers, 2010), 2010)

13

TransTrans--UralianUralian Re-Mo-U ore Province Distribution of U and Re (Dalmatovskoye deposit)

(Khalezov A.B., 2009)

Сontent of rhenium, g/t

14

Geological cross-section

TransbaikalianTransbaikalianReRe--MoMo--UU provinceprovince

HiagdinskoyeHiagdinskoye oreoredepositdeposit

((AccordingAccording toto SosnowskiSosnowski PGO)PGO)

Geological Plan

15

V-U-Mo-precious metals-Re deposit Srednyaya Padma (Karelia, Russia)

http://www.kartravel.ru

Content of Re in ore

- 0.2 g/1000 kg (Savitsky A.V., TitovV.K., Melnikov E.K., 1997)

– 0.01-2.8 g/1000 kg (Troshkina I.D., Yakushenkov N.A., Chekmarev A.M., 2003)

16

Forecast resources of rhenium(objects of infiltration type, Podmoskovnaya uranium-

bearing province)(IMGRE, (IMGRE, KremenetskyKremenetsky АА..АА.).)

Брикетно-Желтухинская Р - 165т 3

Узуновско -Алексеевская Р - 153т 3

НелидовскаяР - 245т 3

Труфаново-Павелецкая Р - 300т 3

СкопинскаяР - 780т 3

ЛьвовскаяР - 290т 3

КалужскаяР - 300т 3

МалинковскаяР - 186т 3

СмоленскаяР - 382 3

Брикетно-ЖелтухинскоеР - 40т Р - 300т (2006г)1 2

АлексеевскоеР - 448т (2005г)2

БельскоеР - 255т (2009г)2

0 60 120 180 км60

17

Re and related components content in the major rock types and their cement (deposit

Belsky) ((data of VSEGEIdata of VSEGEI))Rock, cement, fraction Re Mo U Th V Se Y Sc

Siltsand sandstone

Gross sample 0,86 4,64 123 1,9 95 1,10 8,99 1,74

Clay cement 6,21 55,7 1 840 17,6 1 200 7,19 32,6 14,2

Sulfide cement 1,03 27,2 306 1,93 121 7,63 14,7 2,18

Carbonaceousalevropeschaniki

Gross sample 1,46 17,5 14,20 0,71 14 0,30 9,33 1,19

Clay cement 6,29 127 119 4,79 88,4 2,75 98,9 7,43

Sulfide cement 7,7 237 625 65,7 118 5,93 403 45,7

Carbonaceous silty clay and clay

Gross sample 1,21 125,6 1 281 8,75 1 294,1 - 33,83 10,82

Carbonaceous fraction 0,83 66,1 352 40,5 4 430 3,68 116 19,1

Brown coal rocksGross sample 2,35 22,5 241 5,24 3 651 - 27,6 27,5

Carbonaceous fraction 4,14 80,2 620 11,1 9 760 13,1 66,4 26,3

18

Correlation of the rhenium in the ores with other metals

Correlation of rhenium with other metals in the ores (deposit Belsky)

(data of IMGRE)

19

TREND OF RHENIUM ACCUMULATION IN THE ROCKS

Сlay cement (up to 6.3 g/1000 kg) →Sulphide cement (up to 7.7 g/1000 kg) →

Ultra fraction of sulfides (up to 13.0 g/1000 kg) →Ultra-thin fraction of coal (up to 30.0 g/1000 kg)

Sulfide-carbonaceous cement Coal with microscopic inclusions

of sulfides

Rhenium in the ore bodies found in three forms:oxide, sulphide and native (data of IMGRE)

20

Polymetallic ores classification in terms of productivity(rhenium stock per unit area)

(In-Situ Leaching of Ores / N.P. Laverov et.al. M., 1998)

- Very poor (to 1 g/m2),- Low-productivity (1-5 g/m2),- Ordinary (5-10 g/m2),- Highly (more 10 g/m2)

21

ReS2(solid) + 4.75 O2(g) + 2.5 H2O → ReO4- (liq) +2 SO4

2- (liq) + 5 H+ (liq)

(In-Situ Leaching of Ores / N.P. Laverov et.al. M., 1998)

22(In-Situ Leaching of Ores / N.P. Laverov et.al. M., 1998)

23

Elution of rhenium

Extraction of rhenium (1 stage)

Washing of the extractant

Back extraction of rhenium

Extraction of rhenium (2 stage)

Solid re-extraction of rhenium

Recrystallization of NH4ReO4

Washing of NH4ReO4 by alcohol

Product NH4ReO4

Anion resin AM-p after desorptionU = 0,5 kg/t

Anion resin AM-p

To the sorption of U and Re (au = 0,1 kg/t)Eluate cRe = 10ч15 mg/l

extractW ater

εRe= 60 – 70 %

CRe = 300 mg/l

O : W = 1 : 20rinse water

to the processO : W = 1 : 1 5 - 6 M ammonia

extractant[TAA – 32%; saturated alcohols- 10%; CVS (kerosene) – 58%]

reextractpH 1 – 2O : W = 7 : 1cRe = 1 g/l

raffinate

O : W = 1 : 5εRe = 60%CRe = 8 g/l

extract

25% ammonia

extractant

[TAA – 32%; saturated alcohols -10%; CVS (kerosene) – 58%]

O : W = 10 : 1

Elution of rhenium

Extraction of rhenium (1 stage)

Washing of the extractant

Extraction of rhenium (2 stage)

Solid re-extraction of rhenium

Recrystallization of NH4ReO4

Washing of NH4ReO4 by alcohol

Product NH4ReO4

Anion resin AM-p after desorptionU = 0,5 kg/t

Anion resin AM-p

To the sorption of U and Re (au = 0,1 kg/t)Eluate cRe = 10ч15 mg/l

extractW ater

εRe= 60 – 70 %

CRe = 300 mg/l

O : W = 1 : 20rinse water

to the processO : W = 1 : 1

extractant[TAA – 32%; saturated alcohols- 10%; CVS (kerosene) – 58%]

reextractpH 1 – 2O : W = 7 : 1cRe = 1 g/l

raffinate

O : W = 1 : 5εRe = 60%CRe = 8 g/l

extract

25% ammonia

extractant

[TAA – 32%; saturated alcohols -10%; CVS (kerosene) – 58%]

O : W = 10 : 1

(In-Situ Leaching of Ores / N.P. Laverov et.al. M., 1998)

24

FLOW SHEET FOR RECOVERY OF RHENIUM FROM NITRIC-SULPHURIC SOLUTIONS

NITRIC-SULPHURIC SOLUTION

Rhenium Precipitation

Re-concentrate

Repulpation

Pulp

Ultrafiltration

Rhenium Solution

NaNO3Solution Striping of the Pulp

H2O

StripingSolution

Dissolving ofPolyelectrolyte

Na2SO3 Solution

25

Rhenium deposition by polyelectrolytes from uranium-contained nitrate-sulfate eluates

NH4NO3: (NH4)2SO4 = 1:3, рН-7,2

№ Type PE Rhenium content in filtrate, mg/l /degree of, % by PE:Re (mass.)

4,3 21,7 43,0 130 430

1 АС-392 16,3/2,4 13,9/16,8 14,6/6,8 11,0/34,1 5,5/67,1

2 АС-412 15,0/10,2 13,6/18,6 12,2/26,9 8,4/49,7 4,8/71,3

3 ОП-1-76 - - 13,6/18,6 - 6,1/63,5

4 ОП-3-78 16,7/0 15,8/5,4 15,0/10,2 10,5/37,1 6,0/64,1

5 АП-312 15,5/7,2 16,0/4,2 15,5/7,2 13,4/19,8 9,8/41,3

6 АП-312-2 16,8/0 14,4/13,8 15,0/10,2 12,8/23,4 10,0/40,1

7 АП-392 16,7/0 16,0/4,2 15,8/5,4 10,5/37,1 7,0/58,1

8 АП-400 16,0/4,2 14,2/15,0 13,4/19,8 10,8/35,3 5,3/68,3

9 АП-411-1 16,0/4,2 16,0/4,2 15,8/5,4 15,0/10,2 13,9/16,8

26

RHENIUM SORPTION FROM PRODUCTIVE SOLUTIONS OF UNDERGROUND LEACHING OF URANIUM ORES BY

EXCHANGER OF NEW GENERATION (RUSSIAN FEDERATION)

(Troshkina I.D., Balanovsky N.V., Shilyaev A.V. etc. Chemical Technology, 2011)

Typical pore size distribution in nanostructured ion exchangers

27

Sphericalmicrogranules200 - 400 nm

Predominantpore diameter

100 nm - channelsbetween

microgranules

28

EXTRACTION OF U AND Re

SOLID RE-EXTRACTION

EXTRACTION Re

RE-EXTRACTION OF Re

EXTRACTION OF SCANDIUM

RE-EXTRACTION OF U

RE-EXTRACTION OF SCANDIUM

CLEANING RAFFINATE FROM ORGANIC PHASE

12% solution of NH4OH

18% solution of (NH4)2CO3

Extractant

3% solution of NH4HCO3

Solution of mixture

Raffinate

Solutionof Re

Crystals of (NH4)4UO2(CO3)3

Reextractfor the

production of Re

Reextract for the production of

compounds of Sc

Extractant

(2% solution of ANP-2 + NAF)

Extractant

ExtractNa2CO3 + NaOH

Extractant ( 5% solution of TAA)

PRODUCTIVE SOLUTIONS OF UNDERGROUND LEACHING

TO THE UNDERGROUND LEACHING

29

Lower concentration limitof cost-effective processing

(In-Situ Leaching of Ores / N.P. Laverov et.al. M., 1998)

Element Concentration limit, mg/l

Rhenium 0,2Selenium 10Molybdenum 10Vanadium 40-50Scandium 0,3TR 10

30

(Materialstoday. 2009, V. 12, № 11. – P.13)

Schematic of key components utilizing structural materials in pressurized water fission reactor

31(Materialstoday. 2009, V. 12, № 11. – P.17)

32(Materialstoday. 2009, V. 12, № 11. – P. 32)

33

•phosphonate complexes with 188Re, designed to reduce bone pain associated with metastases due to breast, lung or prostate cancer

•complexes 186, 188Re (V) with dimercaptosuccinic (DMSA) acid for the treatment of medullary thyroid carcinoma

•188Re-sulfur colloid-labeled albumin microspheres for tumors

• 188Re-hydroxyapatite, 188Re-geptasulfid

• 188Re-glyukogeptonat, 188Re-DTPA, intended for coronary angioplasty

•188Re-labeled lipophilic complexes diaminodithiol, Lipiodollabeled with 188Re proposed for the treatment of liver metastases in prostate cancer,

•labeled somatostatin analogue Re-188-RC-160 is considered for the treatment of somatostatin receptor-positive tumors, including breast cancer cells

The use of 188Re isotope in nuclear medicine

34

CONCLUSION

In the implementation of the Nuclear FuelCycle traditional features of associatedrecovery and use of rhenium are saved

- As a trace element Re is recovered fromuranium multicomponent raw materials

- As a metal having high refractoriness Re is used in the heat-resistant alloys for themanufacturing of high-temperaturereactors

35

Thank you for your attention